TW201730195A - Dithiophenethiadiazole semiconductors and related devices - Google Patents

Abstract

The present invention relates to new semiconducting compounds having at least one optionally substituted dithieno[1,2,3]thiadiazole moiety. The compounds disclosed herein can exhibit high carrier mobility and/or efficient light absorption/emission characteristics, and can possess certain processing advantages such as solution-processability and/or good stability at ambient conditions.

Description

Dithiophenothiazole semiconductor and its components

The present invention is directed to a dithiophene thiadiazole semiconductor and its components, and the present application claims priority to U.S. Provisional Patent Application Serial No. 62/276,844, filed on Jan.

The use of flexible and printed electronics for the manufacture of optoelectronic components is a revolutionary new concept, in stark contrast to the need for special and expensive equipment, which utilizes high-volume, inexpensive solution processing (eg printing) Method) on flexible plastic sheets. By using appropriate materials, these technologies enable inexpensive, lightweight, flexible, optically transparent and non-fragmented displays, cell phones, printed batteries, solar cells, and parts for aircraft and satellite structures. The material parts (and other necessary materials) that implement these techniques are semiconductors that undergo charge transfer, absorb light, and/or generate light. In order to expand the function and application of components, two types of semiconductors are required: p-type (hole transmission) and n-type (electron transmission). The use and combination of the two types of semiconductors enable basic electronic components that drive the display, capture light, generate light, perform logic operations, and sense sensor functions.

P-type and n-type channel molecular semiconductors have achieved acceptable component performance and stability. For example, an organic thin film transistor (OTFT) based on acene, oligothiophene (p-type channel), and perylene (n-type channel) exhibits a carrier of more than 1 cm ² /Vs under ambient conditions. Mobility (μ). However, molecular semiconductors are generally more difficult to manufacture by printing than polymer semiconductors due to the viscosity requirements of the solution.

Accordingly, there is a need in the art for new semiconductor compounds, particularly those having good stability, processing characteristics, and/or charge transport characteristics under ambient conditions.

In view of the above, the present invention provides an organic semiconductor compound which can be solved Various deficiencies and shortcomings of the prior art described. The compounds according to the invention exhibit properties such as optimized light absorption, good charge transport properties, good solubility in general solvents, and processing versatility (e.g., by solution processing) under ambient conditions. Therefore, for example, a photovoltaic element of an organic photovoltaic cell (OPV), in combination with one or more compounds of the present invention as a photoactive layer, exhibits high performance under ambient conditions, for example, exhibiting one or more low energy gaps, high fill factor, The performance of high open circuit voltage and high power conversion efficiency preferably shows all criteria. Similarly, other organic semiconductor-based components, such as organic thin film transistors (OTFTs), can be fabricated using the organic semiconductor materials described herein.

In general, the present invention provides a semiconductor compound comprising one or more divalent dithieno[1,2,3]thiadiazole groups. Such a divalent dithieno[1,2,3]thiadiazole group is represented by the following chemical formula (I): Wherein W represents an oxygen group element, and R ¹ represents hydrogen or a substituent thereof. In some embodiments, the compound is a polymer having one or more repeating units M ₁ , each constituent unit M ₁ having at least one dithieno[1,2,3]thiadiazole group, polymerized Degree (n) is at least 3. In some embodiments, the polymer is a homopolymer and comprises only constituent units M ₁ . In other embodiments, the polymer further comprises at least one other constituent unit M ₂ that does not comprise a dithieno[1,2,3]thiadiazole group. Such a constituent unit M ₂ is selected from the following groups: Wherein pi-2, Ar, Z, m, m', m", p and p' are as defined herein. In some embodiments, the compound of the invention is a molecular compound comprising at least one dithiophene [1] a 2,3]thiadiazole group and a plurality of linear or cyclic conjugated groups such that the compound as a whole provides a pi-extension conjugated system.

The present invention provides such compounds and methods of making semiconductor materials based thereon, as well as various compositions, composites and elements of the compounds and semiconductor materials disclosed herein.

The features and advantages of the present invention are apparent from the following description, drawings, and claims.

The following figures are to be understood as illustrative only. The drawings are not necessarily to scale, the &quot The drawings are not intended to be limiting of the scope of the invention.

Figures 1a, 1b, 1c and 1d show four different forms of thin film transistors, Figure 1a shows the bottom gate-top contact, Figure 1b shows the bottom gate-bottom contact, and Figure 1c shows the top gate-bottom contact, Figure 1d Representing a top gate-top contact, each thin film electro-crystalline system is used to incorporate one or more compounds of the invention, particularly as a channel (semiconductor) material.

2 shows a representative construction of a bulk heterojunction organic photovoltaic element (also referred to as a solar cell) incorporating one or more compounds of the invention as a donor and/or acceptor material.

Figure 3 shows a representative construction of an organic light-emitting element incorporating one or more compounds of the invention as electron transport and/or radiation and or hole transport materials.

Throughout the application, a composition having, comprising or comprising a particular constituent or having, comprising or including a particular processing step is contemplated to comprise a composition of the present invention substantially or Including the described construction, the method of the present invention substantially contains or contains the processing steps described.

In the present application, a constituent element or a component is included in the group of constituent elements or constituents listed, and it should be understood that the constituent element or composition may be any constituent element or constituent in the group, or may be selected from two. Or two or more constituent elements or components. Furthermore, the constituent elements and/or features of the compositions, devices, or methods described herein may be arbitrarily combined in various ways, either explicitly or implicitly, without departing from the spirit and scope of the invention.

Terms such as "include, includes, including", "have" (have, has, having), etc., are generally understood to be open-ended and unrestricted.

Unless specifically stated otherwise, the singular terms include the plural (and vice versa). In addition, the term "about" preceding a value generally includes the specified value unless specifically stated otherwise. Here, the term "about" means a variation of ±10% of the standard value unless otherwise stated or implicitly.

The order of the steps or the order in which certain actions are performed is irrelevant as long as the operation can be maintained. Furthermore, two or more steps or actions may be performed simultaneously.

As used herein, "p-type semiconductor material" or "donor" material refers to a semiconductor material, such as an organic semiconductor material, having a hole as the primary current or charge carrier. In some embodiments, when a p-type semiconductor material is deposited on a substrate, it can provide a hole mobility in excess of about 10 ^-5 cm ² /Vs. In the case of field effect devices, a p-type semiconductor material can exhibit a current on/off ratio of more than about 10.

As used herein, "n-type semiconductor material" or "acceptor" refers to a semiconductor material, such as an organic semiconductor material, having electrons as the primary current or charge carriers. In some embodiments, when an n-type semiconductor material is deposited on a substrate, it can provide an electron mobility of more than about 10 ^-5 cm ² /Vs. In the case of field effect devices, an n-type semiconductor material can exhibit a current on/off ratio of more than about 10.

As used herein, "mobility" refers to the measurement of the rate at which a charge carrier passes through a material under the influence of an electric field. For example, a charge carrier is a hole (positive charge) in a p-type semiconductor material, in an n-type semiconductor material. Medium is electron (negative charge). This parameter depends on the architecture of the component and can be measured by field effect components or space charge limiting current measurements.

The compounds used herein are considered to be "environmentally stable" or "safe under environmental conditions". Refers to a transistor that combines the compound as its semiconductor material. After exposure of the compound to environmental conditions, such as air, ambient temperature, and humidity for a period of time, the carrier mobility is maintained at its initial value. For example, a compound may be considered to be environmentally stable. If it is a transistor that incorporates the compound, it exhibits a change in carrier mobility of no more than 20% after exposure to environmental conditions including air, humidity, and temperature for 3, 5, or 10 days. No more than 10% of the initial value.

The fill factor (FF) used herein refers to the ratio of the actual maximum available power (P _m or V _mp *J _mp ) to the theoretical (non-actually available) power ((J _sc *V _oc ). The fill factor can be determined by the following equation: FF = (V _mp * J _mp ) / (J _sc * V _oc ) where J _mp and V _mp represent the current density and voltage at the maximum power point (P _m ), respectively. By changing the resistance in the circuit until J*V is the maximum value; J _sc and V _oc represent the open circuit current and the open circuit voltage respectively. The fill factor is a key parameter for evaluating solar cells. Commercial solar cells usually have about 0.60% or more. Fill factor.

The open circuit voltage (V _oc ) used herein is the potential difference between the anode and cathode of the component without a connected external load.

The power conversion efficiency (PCE) of a solar cell as used herein refers to the percentage of power that is converted from incident light to electricity. The power conversion efficiency (PCE) of a solar cell can be divided by the maximum power point (P _m ) divided by the incident light illuminance (E; W/m ² ) under standard test conditions (STC) and the surface area of the solar cell (A _c ; m ² ) and calculate. STC generally refers to a spectrum at a temperature of 25 ° C, an irradiance of 1000 W/m ² , and an air mass of 1.5 (AM 1.5).

A member (e.g., a film layer) as used herein, if it contains one or more absorbable photons to produce an exciton for generating a photocurrent, can be considered "photoactive".

As used herein, "probable solution processing" means that a compound (eg, a polymer), material, or composition can be used in a solution state, such as spin coating, printing (eg, inkjet printing, gravure printing, lithography, etc.), Spraying method, electrospraying method, drop casting method, dip coating method and blade coating method.

As used herein, "polymeric compound" (or "polymer") refers to a repeating unit of one molecule comprising a plurality of covalently bonded linkages of one or more. A polymer compound (polymer) can be represented by the following general formula: Wherein M represents a repeating unit or a monomer. The polymer may have only one type of repeating unit, and may have two or more kinds of repeating units of different kinds, and may also be referred to as "copolymer" or "copolymer compound". For example, a copolymer compound (copolymer) may contain repeating units Wherein M ^a and M ^b represent different repeating units. Unless otherwise stated, the assembly of repeating units of the copolymer can be head-to-tail, head-to-head or tail-to-tail. Further, the copolymer may be a random copolymer, an alternating copolymer or a block copolymer unless otherwise stated. For example, the general formula: May be used to represent the copolymer having a molar fraction of a copolymer of x and y M ^a mole fraction of M ^a and M ^b M ^b and M ^a monomer copolymerizable with the repeating manner M ^b can be alternating, random , regional random (regiorandom), regional rules or block. In addition to the composition, a polymer compound, in accordance with the measurement technology, by degree of polymerization (n-), molar mass (e.g., number average molecular weight (M _n) and / or the weight average molecular weight (M _w)) is depicted.

As used herein, "heteroatom" refers to elemental atoms other than carbon or hydrogen, including, for example, nitrogen, oxygen, helium, sulfur, phosphorus, and selenium.

As used herein, "halo" or "halogen" means fluoro, chloro, bromo and iodo.

As used herein, "oxo" refers to the oxygen of a double bond (ie, =0).

As used herein, "alkyl" refers to a straight or branched saturated hydrocarbon group. Examples of the alkyl group include methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, t-butyl, 3) Butyl), pentyl (eg, n-pentyl, isopentyl, neopentyl), hexyl, and the like. In certain embodiments, the alkyl group can have from 1 to 40 carbon atoms (i.e., C _{1 -40} alkyl groups), for example, from 1 to 20 carbon atoms (i.e., C _1-20 alkyl groups). In some embodiments, an alkyl group can have from 1 to 6 carbon atoms and can be referred to as a lower alkyl group. Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and isopropyl) and butyl (e.g., n-butyl, isobutyl, t-butyl, and butyl). In some embodiments, an alkyl group as described herein can be substituted. Alkyl groups are generally not substituted by other alkyl, alkenyl or alkynyl groups.

As used herein, "haloalkyl" refers to an alkyl group having one or more halogen substituents. In various embodiments, the haloalkyl group can have from 1 to 40 carbon atoms (i.e., C _1-40 haloalkyl), for example, from 1 to 20 carbon atoms (i.e., C _1-20 haloalkyl). Examples of haloalkyl groups include CF ₃ , C ₂ F ₅ , CHF ₂ , CH ₂ F, CCl ₃ , CHCl ₂ , CH ₂ Cl, and C ₂ Cl ₅ . The perhaloalkyl group, that is, the entire hydrogen atom of the alkyl group, is substituted by a halogen (for example, CF ₃ and C ₂ F ₅ ), and is defined by a haloalkyl group. For example, a C _1-40 haloalkyl group can have the formula: -C _z H _2z+1-t X ⁰ _t , wherein each occurrence of X ⁰ represents F, Cl, Br or I, and z is an integer from 1 to 40, t Is an integer from 1 to 81, and t is less than or equal to 2z+1. A haloalkyl group of a non-perhaloalkyl group can be substituted as described herein.

As used herein, "alkoxy" refers to -O-alkyl. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), 3-butoxy, pentyloxy, hexyloxy and the like. The alkyl group at the -O-alkyl group can be substituted as described herein.

As used herein, "alkylthio" refers to -S-alkyl. These include, but are not limited to, methylthio, ethylthio, propylthio (eg, n-propylthio and isopropylthio), 3-butylthio, pentylthio, hexylthio, and the like. The alkyl group at the -S-alkyl group can be substituted as described herein.

As used herein, "alkenyl" refers to a straight or branched alkyl group having one or more carbon-carbon double bonds. Examples of the alkenyl group include a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a butadienyl group, a pentadienyl group, a hexadienyl group and the like. One or more carbon-carbon double bonds may be internal (for example 2-butene) or terminal (for example 1-butene). In various embodiments, the alkenyl group can have from 2 to 40 carbon atoms (i.e., C _2-40 alkenyl), for example, from 2 to 20 carbon atoms (i.e., C _2-20 alkenyl). In some embodiments, an alkenyl group can be substituted as described herein. Alkenyl groups are generally not substituted by other alkenyl, alkyl or alkynyl groups.

As used herein, "alkynyl" refers to a straight or branched alkyl group having one or more carbon-carbon triple bonds. Examples of alkynyl groups include ethynyl, propynyl, butynyl, pentynyl, hexynyl and the like. One or more carbon-carbon triple bonds may be internal (e.g., 2-butyne) or terminal (e.g., 1-butyne). In various embodiments, an alkynyl group can have from 2 to 40 carbon atoms (i.e., a C _2-40 alkynyl group), for example, from 2 to 20 carbon atoms (i.e., a C _2-20 alkynyl group). In some embodiments, an alkynyl group can be substituted as described herein. Alkynyl groups are generally not substituted by other alkynyl groups, alkyl groups or alkenyl groups.

As used herein, "cyclic group" refers to a carbocyclic or heterocyclic ring comprising one or more (eg, 1-6). In the embodiment, the cyclic group is a "polycyclic group", and the polycyclic group may include two or more mutually fused rings (ie, sharing a common bond) and/or by a snail A ring in which atoms are combined with each other. The cyclic group may be a cycloalkyl group, a heterocyclic group, an aryl group or a heteroaryl group (that is, it may contain only a saturated bond or may contain one or more unsaturated bonds regardless of its aromaticity) and may optionally Substituted as described herein. In the embodiment where the cyclic group is a "monocyclic group", the monocyclic group may include a carbocyclic or heterocyclic ring of 3 to 20 members. The cyclic group may include a C _6-20 aryl group (for example, a C _6-14 aryl group) or a 5-20 membered heteroaryl group (for example, a 5-14 membered hetero atom aryl group), each of which may be selectively The descriptions described herein are replaced.

As used herein, "cycloalkyl" refers to a non-aromatic carbocyclic group, including cyclic alkyl, alkenyl, alkynyl groups. In various embodiments, the cycloalkyl group can contain from 3 to 20 carbon atoms, such as from 3 to 14 carbon atoms (ie, C _3-14 cycloalkyl). A cycloalkyl group can be a monocyclic (e.g., cyclohexyl) or polycyclic (e.g., containing a fused, bridged or helical ring system) wherein the carbon atoms are internal or external to the ring system. The ring position of any suitable cycloalkyl group can be covalently bonded to a defined chemical structure. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, cyclohexadienyl, cycloheptatrienyl, halo Norbornyl, norpinyl, norcaryl, adamantyl and spiro[4.5]decylalkyl and their homologues, isomers, and the like. In some embodiments, a cycloalkyl group can be substituted as described herein.

As used herein, "heterocyclyl" refers to a non-aromatic carbocyclic group containing at least one ring heteroatom selected from the group consisting of O, S, Se, N, P, and Si (eg, O, S, and N). The heterocyclic group may optionally contain one or more double or triple bonds. The heterocyclic group may have 3 to 20 ring atoms, for example, 3 to 14 ring atoms (that is, a 3-14 membered heterocyclic group). One or more of the N, P, S or Se atoms (for example, N or S) in the heterocyclic group may be oxidized (for example, morpholine N-oxide, thiomorpholine S-oxide, thio? Porphyrin S, S-dioxide). In some embodiments, the nitrogen or phosphorus atom of the heterocyclyl can have a substituent, such as a hydrogen atom, an alkyl group, or other substituents described herein. The heterocyclic group may also contain one or more oxy groups such as oxopiperidyl, oxooxazolidyl, dioxo-(1H,3H)pyrimidinyl, oxo-2 ( 2H) Pyridyl group and the like. Examples of heterocyclic groups include morpholine, thiomorpholine, pyranyl, imidazolidinyl, imidazolinyl, oxazolidinyl, pyrazolidinyl, pyrazolinyl, pyrrolidinyl, pyrrolinyl, Tetrahydrofuranyl, tetrahydrothiophenyl, piperidinyl, piperazinyl and the like. In some embodiments, a heterocyclic group can be substituted as described herein.

As used herein, "aromatic group" means an aromatic monocyclic hydrocarbon ring system or one or more aromatic hydrocarbon rings fused (ie, sharing a common bond) together or at least one aromatic monocyclic hydrocarbon ring and one Or a polycyclic ring system in which a cycloalkyl ring and/or a heterocyclic ring are fused. The aryl group may contain 6 to 22 carbon atoms (for example, a C _6-14 aryl group) and may include a plurality of fused rings. In some embodiments, the polycyclic aromatic group can have from 8 to 22 carbon atoms. The ring position of any suitable aryl group can be covalently bonded to a defined chemical structure. Examples of aromatic groups having only an aromatic carbocyclic ring include phenyl, 1-naphthyl (bicyclic), 2-naphthyl (bicyclic), fluorenyl (tricyclic), phenanthryl (tricyclic), and pentacyl (five rings) and so on. Examples of polycyclic systems in which at least one aromatic monocyclic hydrocarbon ring is fused to one or more cycloalkyl rings and/or heterocyclic rings, including benzene derivatives of cyclopentane (ie, fluorenyl, 5,6- Bicycloalkyl/aromatic ring system), benzene derivatives including cyclohexane (ie, tetrahydronaphthyl, 6,6-bicycloalkyl/aromatic ring system), benzene derivatives including imidazolines (ie, benzo) Imidazolinyl, 5,6-bicyclic heterocyclyl/aromatic ring system) and benzene derivatives including pyran (i.e., benzopyranyl, 6,6-bicyclic heterocyclyl/aromatic ring system). Other examples of the aryl group include a benzodioxanyl group, a benzodioxolyl group, a chromanyl group, a porphyrin group, and the like. In some embodiments, an aryl group can be substituted as described herein. In some embodiments, an aryl group can have one or more halogen substituents and can be referred to as a halogen aryl group. The perhaloaryl group, that is, all of the hydrogen atoms in the aryl group are replaced by a halogen atom (for example, -C ₆ F ₅ ), and are included in the definition of a halogen aryl group. In certain embodiments, an aryl group is substituted with another aryl group and may be referred to as a diaryl group. Each aryl group of the diaryl group can be substituted as disclosed herein.

As used herein, "arylalkyl" refers to an alkyl-aryl group wherein the arylalkyl group is covalently bonded to the defined chemical structure via an alkyl group. The arylalkyl group is within the definition of the -YC _6-14 aryl group, and the Y system is as defined herein. An arylalkyl group is, for example, a benzyl group (-CH ₂ -C ₆ H ₅ ). The arylalkyl group can be optionally substituted, i.e., an aryl group and/or an alkyl group, as disclosed herein.

As used herein, "heteroaromatic" means an aromatic monocyclic ring containing at least one ring heteroatom selected from the group consisting of oxygen (O), nitrogen (N), sulfur (S), cerium (Si), and selenium (Se). The system or at least one ring is a polycyclic system that is aromatic and contains at least one ring heteroatom. a polycyclic heteroaryl group comprising two or more heteroaromatic rings fused to each other and a monocyclic heteroaromatic ring fused to one or more aromatic carbocyclic rings, non-aromatic carbocyclic rings and/or non-aromatic heterocyclic rings . The heteroaromatic group may have, for example, 5 to 22 ring atoms as a whole, and may have 1 to 5 ring hetero atoms (for example, a heterocyclic aryl group of 5 to 20 members). A heteroaryl group can be attached to a defined chemical structure at any heteroatom or carbon atom to form a stable structure. Usually a heteroaryl ring does not contain OO, SS or SO bonds. However, one or more of the heteroaryl groups may be oxidized by an N or S atom (e.g., pyridine N-oxide, thiophene S-oxide, thiophene S, S-dioxide). Examples of heteroaromatic groups include, for example, 5- or 6-membered single-ring and 5-6 double-ring systems, as shown below: Wherein T is O, S, NH, N-alkyl, N-aryl, N-(arylalkyl) (eg N-benzyl), SiH ₂ , SiH (alkyl), Si (alkyl) ₂ , Si (arylalkyl) or Si (alkyl) (arylalkyl). Examples of such heteroaromatic rings include pyrrolyl, furyl, thienyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazolyl, tetrazolyl, pyrazolyl , imidazolyl, isothiazolyl, thiazolyl, thiadiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, fluorenyl, isodecyl, benzofuranyl, benzothienyl, quin Polinyl, 2-methylquinolyl, isoquinolyl, quinoxalyl, quinazolyl, benzotriazolyl, benzimidazolyl, benzothiazolyl, benzo Isothiazolyl, benzisoxazolyl, benzooxadiazolyl, benzoxazolyl, cinnolinyl, 1H-carbazolyl, 2H-carbazolyl, indolizinyl , isobenzofuranyl, naphthyridinyl, phthalazinyl, pteridinyl, purinyl, oxazolopyridinyl, thiazolopyridyl, imidazolium Pyridyl, furopyridinyl, thienopyridyl, pyridopyrimidinyl, pyridopyrazinyl, pyridopyridazinyl, thienothiazolyl, thiophene Azolyl, thienoimidazolyl and the like. Further, examples of the heteroaryl group include 4,5,6,7-tetrahydroindenyl, tetrahydroquinolyl, benzothienopyridinyl, benzofuropyridinyl and the like. In some embodiments, a heteroaryl group can be substituted as described herein.

The compounds disclosed herein may comprise a "divalent group", defined herein as a linking group, which forms a covalent bond with two other groups. For example, the compound of the present invention may comprise a divalent C _1-2o alkyl group (e.g., a methylene group), a divalent C _2-20 alkenyl group (e.g., a vinyl group), and a divalent C _2-20 alkynyl group (e.g., an _exetylene group). a divalent C _6-14 aryl group (for example, a phenylene group), a divalent 3-14 membered heterocyclic group (for example, a pyrrolidinyl group), and/or a divalent 5-14 membered heteroaryl group (for example, a thienyl group) ).

The nature of the supply and electron attraction of hundreds of common substituents reflects all common types of substituents that have been identified, quantified and published. The most common quantification of the properties of supplying electrons and attracting electrons is the Hammett value (Hammett σ value). The Hammett σ value of a hydrogen atom is zero, and other substituents have a Hammett σ value, which is a positive or negative increase depending on the electron supply or attraction characteristics. Substituents with a negative Hammett σ value are considered to be electrons, while substituents with a positive Hammett σ value are considered to attract electrons. Refer to the Lange's Handbook of Chemistry, 12th ed., McGraw Hill, 1979, Table 3-12, pp. 3-134 to 3-138, which lists a large number of common Hamilton's σ values, reference The references are incorporated herein.

The term "electron accepting base" should be understood to be synonymous with electron acceptors and electron withdrawing groups. In particular, "electron-withdrawing group (EWG)", "electron accepting group" or "electron acceptor" refers to a hydrogen atom that is functionally located at the same position in the molecule, and attracts electrons more to itself. Examples of electron-withdrawing groups (EWG) include, but are not limited to, halogens (eg, F, Cl, Br, I), -NO ₂ , -CN, -NC, -S(R ⁰ ) ₂ ⁺ , -N(R ⁰ ) ₃ ⁺ , -SO ₃ H, -SO ₂ R ⁰ , -SO ₃ R ⁰ , -SO ₂ NHR ⁰ , -SO ₂ N(R ⁰ ) ₂ , -COOH, -COR ⁰ , -COOR ⁰ , -CONHR ⁰ , -CON(R ⁰ ) ₂ , C _1-40 haloalkyl, C _6-14 aryl, 5- to 14-membered electron-deficient heteroaryl, wherein R ⁰ is C _1-20 alkyl, C _2-20 olefin a C _2-20 alkynyl group, a C _1-20 haloalkyl group, a C _1-20 alkoxy group, a C _6-14 aryl group, a C _3-14 cycloalkyl group, a 3 to 14 membered ring heterocyclic group, Heteroaryl groups of 5 to 14 membered rings, each of which may be optionally substituted as described herein. For example, each C _1-20 alkyl group, C _2-20 alkenyl group, C _2-20 alkynyl group, C _1-20 haloalkyl group, C _1-20 alkoxy group, C _6-14 aryl group, C _{3- a 14-} cycloalkyl group, a 3 to 14 membered ring heterocyclic group, and a 5 to 14 membered ring heteroaryl group may be optionally substituted with a 1-5 small electron withdrawing group such as F, Cl, Br, -CN, - NC, -S(R ⁰ ) ₂ ⁺ , -N(R ⁰ ) ₃ ⁺ , -SO ₃ H, -SO ₂ R ⁰ , -SO ₃ R ⁰ , -SO ₂ NHR ⁰ , -SO ₂ N(R ⁰ ₂ , -COOH, -COR ⁰ , -COOR ⁰ , -CONHR ⁰ , -CON(R ⁰ ) ₂ .

The term "electronic-based" should be understood to be synonymous with electronic donors. In particular, "electron-donating" or "electron donor" refers to a hydrogen atom having a functional group at the same position in the molecule, and supplying electrons to adjacent atoms. Examples of electron-donating groups include -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ , -N(R ⁰ ) ₂ and an electron-rich heteroaryl group of 5 to 14 member rings, wherein R ⁰ is C _1-20 Alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-14 aryl or C _3-14 cycloalkyl.

Various unsubstituted heteroaryl groups can be considered as electron rich (π-excess) or electron deficient (π-deficient). Such classification is based on the average electron density of each ring atom compared to the carbon atom on the benzene ring. The electron rich system comprises a 5-membered heteroaryl group having one hetero atom, such as furan, pyrrole, thiophene and its benzo counterparts, such as benzofuran, benzopyrrole and benzothiophene. Electron-deficient systems include 6-membered heteroaryl groups having one or more heteroatoms, such as pyridine, pyrazine, pyridazine, and pyrimidine, and benzo counterparts thereof, such as quinoline, isoquinoline, quinoxaline, anthracene Porphyrin, pyridazine, naphthyridine, quinazoline, phenanthridine, acridine and hydrazine. The mixed heteroaromatic ring may belong to any class depending on the kind, number and position of one or more heteroatoms in the ring. Reference to heterocyclic chemistry (Katritzky, AR and Lagowski, JM, Heterocyclic Chemistry , John Wiley & Sons, New York, 1960).

In the present specification, the substituents of the monomers A and B are disclosed in groups or ranges. In particular, the description includes each and every individual sub-combination of the members of the group or range. For example, the term "C _1-6 alkyl" specifically discloses C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₁ - C ₆ , C ₁ - C ₅ , C ₁ - C4, C ₁ -C ₃ , C ₁ -C ₂ , C ₂ -C ₆ , C ₂ -C ₅ , C ₂ -C ₄ , C ₂ -C ₃ , C ₃ -C ₆ , C ₃ -C ₅ , C ₃ -C ₄ , C ₄ -C ₆ , C ₄ -C ₅ and C ₅ -C ₆ alkyl. As other examples, integers ranging from 0 to 40, specifically, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 are separately disclosed. , 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 and 40, and range 1 An integer of ~20, specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 are separately disclosed. Further examples include the phrase "optionally substituted with 1-5 substituents", specifically intended to be disclosed separately, including 0, 1, 2, 3, 4, 5, 0-5, 0-4, 0. -3, 0-2, 0-1, 1-5, 1-4, 1-3, 1-2, 2-5, 2-4, 2-3, 3-5, 3-4, and 4-5 The chemical group of a substituent.

The compounds described herein may comprise an asymmetric atom (also referred to as a palm center), and some compounds may contain two or more asymmetric atoms or centers which may produce optical isomers (enantiomers) and Enantiomer (geometric isomer). The present invention includes such optical isomers and diastereomers, including each of the resolved enantiomerically or diastereomericly pure isomers (e.g., (+) or (-) stereoisomers) and such Spin the mixture, as well as other enantiomers and mixtures of diastereomers. In some embodiments, optical isomers can be obtained in a form enriched in enantiomers or pure enantiomers by standard procedures well known in the art, including, for example, palm separation, diastereomeric salt formation. , kinetic segregation and asymmetric synthesis. The invention also includes cis and trans isomers containing alkenyl groups such as alkenes, azo and imines. It will be understood that the compounds of the invention include all possible pure or mixed regioisomers. It is possible to isolate such isomers, for example using standard separation procedures well known in the art, such as column chromatography, thin layer chromatography, simulated moving bed chromatography, high performance liquid chromatography. However, mixtures of regioisomers can be used for purposes similar to each of the individual regioisomers.

The description of a regioisomer specifically includes any other regioisomer and any mixture of regioisomers unless specifically stated otherwise.

As used herein, "leaving group" means a charged or uncharged atom (or group of atoms) which, for example, may be substituted into a stable species due to a substitution or removal reaction. Examples of leaving groups include, but are not limited to, halogen (eg, Cl, Br, I), azide (N ₃ ), thiocyanate (SCN), nitro (NO ₂ ), cyanate (CN), water (H ₂ O), ammonia (NH ₃ ), and sulfonic acid groups (eg, OSO ₂ -R, wherein R can be a C _1-10 alkyl group or a C _6-14 aryl group, each optionally being selected from C _a 1-4 alkyl group of a _1-10 alkyl group and an electron withdrawing group), a sulfonic acid group such as toluenesulfonate (OTs), methanesulfonate (OMs), p-bromobenzenesulfonate (OBs), 4-Nitrobenzenesulfonate (ONs) and trifluoromethanesulfonate (OTf).

Throughout the specification, the structure may or may not be represented by a chemical name. if In case of any naming problem, the structure shall prevail.

This invention relates to molecules or polymer compounds useful in organic semiconductor materials. The compounds of the present invention have good solubility in various usual organic solvents and good stability in air. The compounds of the present invention can impart a variety of desirable properties when incorporated into optical, electronic or optoelectronic components including, but not limited to, organic photovoltaic or solar cells, organic light emitting diodes, and organic field cells.

More specifically, the invention provides a semiconductor compound comprising one or more groups of formula (I): Wherein W is selected from the group consisting of S, Se, and Te; and each R ^{1 is} independently selected from the group consisting of H, halogen, -CN, NO ₂ , R ² , -LR ³ , OH, OR ² , OR ³ , NH ₂ , NHR ² , N(R ² ) ₂ , NR ² R ³ , N(R ³ ) ₂ , SH, SR ² , SR ³ , S(O) ₂ OH, -S(O) ₂ OR ² , -S(O ₂ OR ³ , C(O)H, C(O)R ² , C(O)R ³ , C(O)OH, C(O)OR ² , C(O)OR ³ , C(O)NH ₂ , C(O)NHR ² , C(O)N(R ² ) ₂ , C(O)NR ² R ³ , C(O)N(R ³ ) ₂ , SiH ₃ , SiH(R ² ) ₂ , a group of SiH ₂ (R ² ) and Si(R ² ) ₃ , wherein L is selected from the group consisting of divalent C _1-40 alkyl, divalent C _2-40 alkenyl, divalent C _1-40 haloalkyl, and a valence group; each R ^{2 is} independently selected from the group consisting of C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl, and C _1-40 haloalkyl; each R ^{3 is} independently Selected from the group consisting of a C _3-10 cycloalkyl group, a C _6-14 aryl group, a C _6-14 haloaryl group, a 3-12 membered heterocycloalkyl group, and a 5-14 membered heteroaryl group, which are optionally selected The ground is substituted with from 1 to 5 substituents selected from the group consisting of halogen, -CN, NO ₂ , R ² , OR ² and SR ² .

In a preferred embodiment, one or more groups of formula (I) are shown. Optionally by formula (II): Substituted dithieno[1,2,3]thiadiazole groups are shown wherein R ¹ is as defined herein. For example, R ¹ may be selected from the group consisting of F, Cl, -CN, NO ₂ , R ² , OR ² and SR ² wherein R ² is selected from a linear or branched C _1-40 alkyl group, straight A chain or branched C _2-40 alkenyl group and a linear or branched C _1-40 haloalkyl group. In other embodiments, R ¹ is H and the one or more groups of formula (I) are of formula (III): An unsubstituted dithieno[1,2,3]thiadiazole group is shown.

In some embodiments, the compound of the invention is a polymer having one or more repeating units M ₁ wherein each constituent unit M ₁ has at least one group of formula (I), the polymerization of the polymer Degree (n) is at least 3.

In addition to the group represented by the formula (I), the repeating unit M ₁ may include one or more spacers (Sp), which may be acyclic (Z) or cyclic, particularly monocyclic (Ar) or polycyclic (pi-2), together with the group represented by the formula (I), can provide a pi-extension conjugated group. For example, M ₁ may be selected from the following groups: Wherein pi-2 is a selectively substituted conjugated polycyclic group; each occurrence of Ar is independently a selectively substituted 5- or 6-membered aryl or heteroaryl; Z is conjugated acyclic a linker; m and m' are independently 0, 1, 2, 3, 4, 5 or 6, but at least one of m and m' is not 0; p and p' are independently 0 or 1, but p and p At least one of ' is 1.

The conjugated polycyclic group pi-2 may be illustrated as a selectively substituted C _8-26 aryl group or an 8-26 membered heteroaryl group. For example, pi-2 can have a planar and pi-extended conjugated ring center that can be selectively substituted as disclosed herein. Examples of suitable ring centers include naphthalene, anthracene, tetraphenylene, pentacene, anthracene, anthracene, coronene, fluorene, indacene, indenofluorene, and four. The tetraphenylene and one or more of the carbon atoms are changed to analogs of heteroatoms such as O, S, Si, Se, N or P.

In some embodiments, pi-2 can be selected from the group consisting of:

Wherein R ^a is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C(O)R, -OC(O)R, and -C(O)OR; R ^b Is selected from the group consisting of H, R and -LR ^f ; R ^c is H or R; R ^d is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C (O) R, -OC(O)R, -C(O)OR, and -LR ^f ; R ^e is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, - C(O)R, -OC(O)R, -C(O)OR and ^Rf ; ^Rf is a _C6-20 aryl group or a 5-20-membered heteroaryl group, each being selectively selected from 1-8 base substitutions of the F, Cl, -CN, R, -OR, and -SR groups; L is selected from the group consisting of -O-, -S-, -C(O)-, -OC ( O)-, -C(O)O- and a covalent bond; and R is selected from the group consisting of C _1-40 alkyl, C _1-40 haloalkyl, C _2-40 alkenyl, and C _{2- 40} alkynyl.

The monocyclic conjugated group Ar, at each occurrence, is independently substituted 5- to 6-membered (hetero) aryl. For example, Ar may be selected from the group consisting of phenyl, thienyl, thiazolyl, isothiazolyl, thiadiazolyl, furyl, oxazolyl, isoxazolyl, oxadiazolyl, pyrrolyl, tri An azolyl, tetrazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidinyl, pyridazinyl and pyrazinyl group, each optionally being selected from the group consisting of halogen, CN, C _1-40 alkyl, C ₁ 1-4 R ⁵ groups of _-40 haloalkyl, C _1-40 alkoxy and C _1-40 alkylthio groups are substituted.

By way of example, when each Ar in (Ar) _m and/or (Ar) _m' is present (ie, when m and m' are 1, 2, 3, 4, 5 or 6): Wherein each X is independently selected from the group consisting of N, C and CR ⁴ , wherein R ⁴ is selected from the group consisting of F, Cl, -CN, R ² , OR ² , SR ² , C(O)R ² , OC(O)R ² and C(O)OR ² , wherein R ² is as defined herein. Further, when (Ar) _m and/or (Ar) _{m' is} present, it is selected from the following groups: Wherein each R ^{4 is} independently selected from the group consisting of F, Cl, CN, R ² , OR ² and SR ² , wherein R ² is a linear or branched C _1-40 alkyl or haloalkyl group.

The conjugated acyclic linker Z may include one or more double or triple bonds. For example, Z may be a divalent vinyl group (ie, having one double bond), a divalent ethynyl group (ie, having one triple bond), including two or more conjugated double or triple bonds or other straight chain or branch. The chain may include a C _4-40 alkenyl or alkynyl group of a conjugated system of a hetero atom such as Si, N, P or the like. In a particular embodiment, Z is selected from the group consisting of:

In a preferred embodiment, the polymer of the invention comprises a repeating unit M ₁ selected from the group consisting of: Wherein Ar, R ¹ , W, m and m' are as defined herein.

More desirably, M ₁ is selected from the group consisting of: Wherein R ⁴ is selected from the group consisting of R ² , OR ² and SR ² , and R ² is a linear or branched C _1-40 alkyl or haloalkyl group.

In certain embodiments, the polymer of the present invention is a homopolymer comprising only the same repeating unit M ₁ . In other embodiments, the polymer is a copolymer, comprising of two or more different repeating units M _1. Also in other embodiments, the present invention is a polymer comprising at least one of M ₁ and M other repeating units of the copolymer _2, wherein the repeating unit of formula M ₂ does not contain any (I) at least one group of the repeating unit. Such repeating unit M ₂ comprises one or more acyclic (Z), monocyclic (Ar) and/or polycyclic (pi-2) conjugated linkers which together provide a pi-extension conjugated group. For example, M ₂ is selected from the following groups: Wherein pi-2, Ar, Z, m, m', m", p and p' are as defined herein.

To illustrate, in certain embodiments, M ₂ can have the following chemical formula: Wherein, m "is selected from 2, 3 or 4; and Ar are as defined herein based e.g. M ₂ is selected from the group: Wherein, for example, each R ^{4 is} independently selected from the group consisting of R ² , OR ² and SR ² , wherein R ² is a linear or branched C _1-40 alkyl or haloalkyl group.

In other embodiments, M ₂ can have the following chemical formula: Wherein pi-2 can be selected from the group consisting of:

Wherein R ^a is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C(O)R, -OC(O)R, and -C(O)OR; R ^b Is selected from the group consisting of H, R and -LR ^f ; R ^c is H or R; R ^d is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C (O) R, -OC(O)R, -C(O)OR, and -LR ^f ; R ^e is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, - C(O)R, -OC(O)R, -C(O)OR and ^Rf ; ^Rf is a _C6-20 aryl group or a 5-20-membered heteroaryl group, each being selectively selected from 1-8 base substitutions of the F, Cl, -CN, R, -OR, and -SR groups; L is selected from the group consisting of -O-, -S-, -C(O)-, -OC ( O)-, -C(O)O- and a covalent bond; and R is selected from the group consisting of C _1-40 alkyl, C _1-40 haloalkyl, C _2-40 alkenyl, and C _{2- 40} alkynyl.

In still other embodiments, M ₂ can have the following chemical formula: Wherein Ar, pi-2, m and m' are as defined herein. Preferably, (Ar) _m and (Ar) _m' are selected from the group consisting of: Wherein R ⁴ is as defined herein, and pi-2 is selected from the group consisting of:

Wherein R ^a is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C(O)R, -OC(O)R, and -C(O)OR; R ^b Is selected from the group consisting of H, R and -LR ^f ; R ^c is H or R; R ^d is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C (O) R, -OC(O)R, -C(O)OR, and -LR ^f ; R ^e is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, - C(O)R, -OC(O)R, -C(O)OR and ^Rf ; ^Rf is a _C6-20 aryl group or a 5-20-membered heteroaryl group, each being selectively selected from 1-8 base substitutions of the F, Cl, -CN, R, -OR, and -SR groups; L is selected from the group consisting of -O-, -S-, -C(O)-, -OC ( O)-, -C(O)O- and a covalent bond; and R is selected from the group consisting of C _1-40 alkyl, C _1-40 haloalkyl, C _2-40 alkenyl, and C _{2- 40} alkynyl.

In other embodiments, M ₂ can have the chemical formula shown in the following group: Wherein m, m' and m" are independently 1, 2, 3 or 4; and Ar, pi-2 and Z are as defined herein. In such an embodiment, M ₂ may be selected from the group consisting of: Wherein R ⁴ is as defined herein.

In a preferred embodiment, the polymer of the present invention is a copolymer of M ₁ and at least one M ₂ wherein M ₂ is selected from the group consisting of: Wherein pi-2, Ar, m, m', m" are as defined herein.

Certain embodiments of the polymers of the present invention may be represented by a chemical formula selected from the group consisting of: Wherein M _1A and M _1B represent different repeating units M ₁ ; M _2A and M _2B represent different repeating units M ₂ ; x and y are real numbers representing the molar ratio; n is the degree of polymerization. To illustrate, M _1A and M _1B are different units selected from the group consisting of: Wherein R ⁴ is selected from the group consisting of R ² , OR ² and SR ² , wherein R ² is a linear or branched C _1-40 alkyl or haloalkyl group. Further, M _2A and M _2B can be: and and and and and ; or 2 repeat units are represented by: Where M _2A is Ar And in M _2B , Ar is

For each of the above polymers, the degree of polymerization (n) may be an integer of from 3 to 1,000. In some embodiments. n can be 4 to 1,000, 5 to 1,000, 6 to 1,000, 7 to 1,000, 8 to 1,000, 9 to 1,000, and 10 to 1,000. For example, n can be 8~500, 8~400, 8~300 or 8~200. Examples of compounds of the invention comprising two or more different repeating units, having such repeating units in a random or alternating repeating manner, and having a molar ratio of two repeating units of from about 0.05 to 0.95 . For example, the corresponding molar ratios (x and y) of the two repeating units may be in the range of about 0.1 to 0.9, in the range of about 0.2 to 0.8, in the range of about 0.3 to 0.7, in the range of about 0.4 to 0.6, and about 0.45 to 0.55. The scope. In certain embodiments, the polymer can have the same first repeat unit and second repeat unit (ie, x = y = 0.5).

In some embodiments, the compound is a molecular compound comprising at least one group of formula (I) and a plurality of linear and/or cyclic conjugated groups whereby the compound provides a pi-extension conjugate system .

To illustrate, the exemplified small molecule semiconductor compound includes at least one group of formula (I), and desirably one or more groups of formula (I) are represented by formula (II) for use in preparing the formulations described herein. The monomer of the polymer can be represented by the following chemical formula: Wherein Q ¹ may be X ¹ or T ¹ , and Q ² may be X ² or T ² , wherein X ¹ and X ² may be the same or different reactive groups, such as halides, organotin radicals, boric acid esters or polymerizable And T ¹ and T ² may be the same or different terminal groups selected from the group consisting of H, R ² and C(O)R ² wherein R ² is C _1-40 alkyl or haloalkyl And pi-2, Ar, Z, m, m', m", p and p' are as defined herein.

Certain embodiments of the molecular semiconducting compound according to the present invention may be represented by the chemical formula of the following group: Wherein R ¹ , R ² , m and m′ are as defined herein.

Specific embodiments of the molecular semiconductor compound exemplified in accordance with the present invention include:

The semiconductor compounds and monomers comprising the groups of formula (I) exemplified in accordance with the invention can be prepared using the synthetic routes described below. Other monomers in accordance with the present invention may be commercially available, or known in the literature, or may be prepared from readily available intermediates using standard synthetic procedures or procedures well known to those skilled in the art. Standard synthetic methods and processes for the preparation of organic molecules, functional group conversion and manipulation are readily available from relevant scientific literature or standard textbooks in the field.

To illustrate, the unsubstituted dithieno[1,2,3]thiadiazole group is according to, but not limited to, the literature (see, for example, Trusova, ME et al., Synthesis , 13: 2154-2158 (2011); Ward , ER et al., J. Chem. Soc. , 2374-2379 (1962); and Hünig, S. et al., Justus Liebigs Annalen der Chemie , 738: 192-194 (1970)) Benzene-like [1, 2,3] The synthetic route of benzozenazole (benzenoid [1,2,3]thiadiazole), which can be closed by diazotization (formation of a diazo compound), for example: And synthesis.

Other ways are summarized as follows:

Alkyl-substituted dithieno[1,2,3]thiadiazoles can be synthesized according to the following formula: It is noted that 4-alkyl-3-aminothiophene can be prepared using the process described by Zhang et al. (Zhang et al. , Organic Letters , 16(9): 2522-2525 (2014); 4-alkyl- 3-Mercaptothiophene can be prepared using the procedure described by Flammang et al. (Flammang et al. , Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry , 7: 1261-1264 (1997)).

Since the reaction intermediate is a diazonium salt, any reagent which can form an aromatic diazonium salt from an aromatic amine can be used for the preparation of a dithieno[1,2,3]thiadiazole ring and its derivatives. An example of the manner of diazotization can be found in the literature (Butler, RN, Chemical Reviews , 75(2): 241-257 (1975) and O'Leary, P., Sci. Synth. , 31b, 1361-1400 (2007). )) found in).

Compounds known in the following literature may be synthesized in the following manner: and Commercially available; It can be synthesized using the process described by Gol'dfarb (Gol'dfarb et al. , Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya , 10: 2290-5 (1973)); It can be synthesized using the process described by Kellogg (Kellogg et al. , Journal of Organic Chemistry , 33(7): 2902-9 (1968)); The reaction can be carried out using the method described by Barbarella (Barbarella et al. , Tetrahedron , 53 (27): 9401-9406 (1997)); The reaction can be carried out using a similar method as described (Sabbatini et al. , Journal of Medicinal Chemistry , 53(17): 6506-6510 (2010)); The reaction can be carried out using a similar method as described (Qiu et al. , Angewandte Chemie, International Edition , 52(44): 11581-11584 or Al-Allaf et al. , Journal of Organometallic Chemistry , 373(1): 29- 35 (1989)); It can be synthesized using the process described by Mahatesekake (Mahatsekake et al. , Sulfur Letters , 7(6): 231-8 (1988)); The reaction can be carried out using the process described by Ishii (Ishii et al. , Heteroatom Chemistry , 25(6): 658-673 (2014)); It can be synthesized using the process described in U.S. Patent Application Serial No. 14/951,628.

An unsubstituted dithieno[1,2,3]thiadiazole which can then be halogenated or otherwise provided with a reactive group (Q) to render it with the various Sp groups described herein (Ar, Z and/or Pi-2) coupling. For example, monohalogenated dithieno[1,2,3]thiadiazole derivatives have small molecule semiconductors or regioregular polymers for dithieno[1,2,3]thiadiazolyl groups.

To illustrate, dithieno[1,2,3]thiadiazole can be brominated to provide a monobrominated or dibrominated derivative, which is then used in combination with other dithieno[1,2,3]thiadiazoles. And/or different conjugated groups having complementary reactive groups are coupled to provide various molecules and polymer semiconductors in accordance with the present invention.

For example, monobrominated dithieno[1,2,3]thiadiazoles can be synthesized from the corresponding precursors using conventional bromination methods using a stoichiometry of the halogen to optimize monobromination: Further, since two isomers can be formed, the ratio of the two compounds can be controlled by changing experimental conditions such as temperature, time, concentration, solvent, and brominating reagent.

An alternative route to monobrominated dithieno[1,2,3]thiadiazole is to construct a thiadiazole ring by diazotization starting from a monobrominated derivative: From the monobrominated dithieno[1,2,3]thiadiazole derivatives, comprising two groups of formula (I) and one or more linear and or cyclic conjugated groups (below The dimer represented by M ₂ ) can be synthesized as follows:

Dithieno[1,2,3]thiadiazole dibromide can be synthesized from the corresponding precursor using conventional bromination methods using a stoichiometry of 2 times halogen to optimize dibromination, for example

Similar to the monobrominated version, it is possible to construct a thiadiazole ring from diazotium dithiophene thiol by diazotization:

For the compounds of the invention, there are M ₁ units: As an example of a polymer, dithieno[1,2,3]thiadiazole is brominated or derivatized with a reactive group and serves as a key component.

Other polymerizable derivatives of dithieno[1,2,3]thiadiazole, including dimethyltinylated dithieno[1,2,3]thiadiazole and diborated dithieno[1] , 2, 3] thiadiazole. Dimethyltinated dithieno[1,2,3]thiadiazole derivatives can be synthesized according to the following formula: The conditions for catalyst tin alkylation are well known in the art (for example, see Woo, CH et al., JACS , 130(48): 16324-16329 (2008)). The diborated dithieno[1,2,3]thiadiazole derivative can be synthesized according to the following formula: The conditions for catalyst boration are well known in the art (for example, see Zhao, Y. et al., Tetrahedron , 68(44): 9113-9118 (2012)).

Brominated or metallated dithieno[1,2,3]thiadiazole derivatives can be used as M ₁ units to copolymerize with M ₂ units having complementary reactive groups. Alternatively, the brominated or metallated dithieno[1,2,3]thiadiazole derivative can be reacted with one or more Sp groups having complementary reactive groups to provide a pi-extended semiconductor compound. Suitable complementary reactive groups for use in various coupling or polymerization reactions are well known in the art. In particular, it can be used as described in Yamamoto et al. (Yamamoto, J. Organomet. Chem . , 653: 195-199 (2002), Walton et al. , Polymer Chemistry (Fred J. Davis ed. 2004), p. 158- 187 and Stillchole et al. , Macromolecular Rapid Communications , 28(4): 387-394 (2007)) Still coupling or Suzuki coupling reaction.

M ₁ and polymerized with the element M ₁ and M ₂ the copolymerization, may be by various conventional in the art to achieve a reaction, comprising a process similar to Yamamoto et al of the document (Yamamoto, J.Organomet.Chem, 653.: 195-199 (2002), Walton et al. , Polymer Chemistry (Fred J. Davis ed. 2004), p. 158-187 and Galbrecht et al. , Macromolecular Rapid Communications , 28(4): 387-394 (200) The entire disclosure is hereby incorporated by reference in its entirety for all purposes. In particular, a Stille coupling or a Suzuki coupling reaction can be used to prepare a high molecular weight and a high yield according to the present invention ( 75%) of the polymer compound was confirmed by ¹ H NMR spectroscopy, elemental analysis and/or GPC measurement. Can be reacted in the following manner outlined several embodiments for M or M ₁ itself and the polymerization of copolymerization of M _{2 1} illustrated. It is to be understood that polymerizable groups (for example, SnR ₃ , BR ₂ , MgX, ZnX and Br, X is a halogen and R is an alkyl group) can be reversed between M ₁ and M ₂ . A similar reaction can be used for the coupling of a group of formula (I) with an Ar, pi-2 and/or X group to provide a group other than formula (I) such as Ar, pi-2 and/or X. Repeat unit M _{1 of the} group.

The coupling shown below illustrates the coupling of a dithiophene[1,2,3]thiadiazole derivative of dibromide with a dimetalated derivative of the pi-2 group:

The reactions described below can be similarly used for the coupling of a dithieno[1,2,3]thiadiazole derivative of dibromide with a Sp group having a complementary reactive group to provide a more extended M ₁ unit, E.g: For example, a dithieno[1,2,3]thiadiazole derivative dibromide can be coupled with two R ³ substituted thienyl groups to provide a monomer: It can be used for the copolymerization of the repeating unit pi-2 as shown below, wherein R ³ is a C ₁₂ alkyl group:

Other possible syntheses of other polymers according to the invention are illustrated in the following manner:

Without wishing to be bound by any particular theory, it is believed that the polymers of the present invention having a regioregular polymer backbone can result in higher molecular weights, more π-conjugated structures, and thus better charge transport efficiency. Thus, in the preparation of the polymers of the invention, the invention may comprise isolating a particular average molecular weight fraction, and/or enriching and/or isolating M ₁ and/or M ₂ having two or more stereoisomers. Specific stereoisomers.

The preparation of the polymer of the present invention is carried out using a coupling reaction similar to that described above, and the various molecular semiconducting compounds according to the present invention may be mono- or di-halogenated/metal by different dithieno[1,2,3]thiadiazoles. The derivative is prepared by reacting with a spacer, as explained below:

The semiconductor compounds disclosed herein are stable under ambient conditions (environmentally stable) and are soluble in common solvents. As used herein, a compound is considered to be electrically "environmentally stable" or "environmentally stable" when it is exposed to environmental conditions such as air, ambient temperature and humidity for a period of time. The mobility is maintained at its initial value. For example, a compound according to the invention may be considered to be environmentally stable, exhibiting a change in carrier mobility of no more than 20% or no more than 10% after exposure to environmental conditions including air, humidity and temperature for 3, 5 or 10 days. The initial value. In addition, a compound can be considered to be environmentally stable. If it is absorbed by the corresponding film, it does not change by more than 20% after exposure to environmental conditions including air, humidity and temperature for 3 days, 5 days or 10 days. The initial value of the change is no more than 10%).

The OTFT based on the compound of the present invention can have long-term operability and sustained high performance under ambient conditions. For example, OTFTs based on certain embodiments of the compounds of the present invention can maintain satisfactory component performance in high humidity environments. Certain embodiments of the compounds of the invention may also exhibit excellent thermal stability over a wide range of annealing temperatures. Photovoltaic components can maintain satisfactory power conversion efficiency over extended periods of time.

As used herein, when at least 0.1 mg of the compound is soluble in 1 mL of the solvent, the compound can be considered to be soluble in 1 mL of the solvent. Examples of common organic solvents include petroleum ether; acetonitrile; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as acetone and methyl ethyl ketone; such as tetrahydrofuran, dioxane, and bis ( An ether of 2-methoxyethyl)ether, diethyl ether, diisopropyl ether and a third butyl methyl ether; an alcohol such as methanol, ethanol, butanol or isopropanol; an aliphatic hydrocarbon such as hexane Such as methyl acetate, ethyl acetate, methyl formate, ethyl formate, isopropyl acetate and butyl acetate; such as dimethyl carbamide and dimethyl acetamide amide; Anthracene of dimethyl hydrazine; such as dichloromethane, chloroform, dichloroethane, chlorobenzene, dichlorobenzene and Halogenated aliphatic and aromatic hydrocarbons of trichlorobenzene; and cyclic solvents such as cyclopentanone, cyclohexanone and 2-methylpyrrolidone. The compounds of the present invention may have a solubility of up to 60 g/L at room temperature in typical organic solvents such as xylene, dichlorobenzene (DCB) and other chlorinated hydrocarbons (CHC).

The compounds of the present invention can be fabricated into a variety of articles using solution processing techniques in addition to other more expensive processes such as vapor deposition. Various solution processing techniques have been used in organic electronics. Common solution processing techniques include, for example, spin coating, drop casting, zone casting, dip coating, knife coating or spray coating. Another example of solution processing techniques is printing. As used herein, "printing" includes non-contact methods such as inkjet printing, micro-distribution, and the like, as well as screen printing, gravure printing, offset printing, flexographic printing, lithography, pad printing, microcontact printing gravure, and the like. Contact method.

The compounds of the present invention are useful in the preparation of semiconductor materials (e.g., compositions and composites) which in turn can be used in the manufacture of various articles, structures, and components. In some embodiments, a semiconductor material incorporating one or more compounds of the present invention can exhibit n-type semiconductor activity, bipolar activity, light absorption, and luminescence.

Accordingly, the present invention further provides methods of making semiconductor materials. The method can include preparing a composition comprising one or more of the compounds disclosed herein dissolved or dispersed in a liquid medium such as a solvent or solvent mixture, depositing the composition on a substrate to provide a semiconductor material precursor, and processing ( The semiconductor precursor is, for example, heated to provide a semiconductor material (e.g., a thin film semiconductor) comprising the compounds disclosed herein. In various embodiments, the liquid medium can be an organic solvent, an inorganic solvent such as water, or a combination thereof. In some embodiments, the composition may further comprise independently selected from the group consisting of a viscosity modifier, a detergent, a dispersant, a binder, a compatibilizer, a hardener, an initiator, a humectant, an antifoaming agent, and a wetting agent. One or more additives in the group of wetting agents, pH adjusters, biocides, and bacteriostats. For example, a surfactant and/or a polymer (for example, polystyrene, polyethylene, poly-α-methylstyrene, polyisobutylene, polypropylene, polymethyl methacrylate, etc.) may be included as a dispersing agent and a binder. , compatibilizer and / or defoamer. In some embodiments, the deposition step can be performed by a printing process including inkjet printing and various contact printing techniques such as screen printing, gravure printing, offset printing, pad printing, lithography, flexographic printing, and microcontact printing. In other embodiments, the deposition step can be applied by spin coating, drop casting, zone casting, dip coating, knife coating Fabric or spray method implementation.

Various products include electronic components, optical components, and optoelectronic components, such as thin film semiconductors, field effect transistors (eg, thin film transistors), photovoltaics, photodetectors, such as organic light emitting diodes (OLEDs), and organic light emitting transistors ( OLET) organic light-emitting elements, complementary metal oxide semiconductors (CMOS), complementary inverters, diodes, capacitors, perceptrons, D flip-flops, rectifiers, and ring oscillators, which use the compounds of the present invention Methods of preparing these are included within the scope of the invention. The compounds of the present invention may provide processing and handling advantages in the manufacture and/or use of such elements. For example, articles of various elements as described herein can include composite materials having the semiconductor materials of the present invention and substrate members and/or dielectric members. The substrate member may be selected from the group consisting of doped germanium, indium tin oxide (ITO), ITO coated glass, ITO coated polyimide or other plastic, alone or coated on a polymer or other substrate. Aluminum or other metals, doped polythiophenes, and the like. The dielectric member may be made of an inorganic dielectric material such as various oxides (for example, SiO ₂ , Al ₂ O ₃ , HfO ₂ ), such as various polymer materials (for example, polycarbonate, polyester, polystyrene, polyhalogenated). Organic dielectric materials of ethylene and polyacrylates and self-assembled superlattice/self-assembled nano dielectric (SAS/SAND) materials (eg, Yoon et al., PNAS, 102(13): 4678-4682 (2005) The entire disclosure of which is incorporated herein by reference, and the disclosure of the entire disclosure of the entire disclosure of the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the entire disclosure of In some embodiments, the dielectric member can include crosslinked polymer blends as described in U.S. Patent Application Serial Nos. The composite may also include one or more electrical contacts. Suitable materials for source, drain and gate electrodes, including metals (such as Au, Al, Ni, Cu), transparent conductive oxides (such as ITO, IZO, ZITO, GZO, GIO, GITO) and conductive polymers ( For example, poly(3,4-ethylenedioxythiophene) poly(styrene sulfonate) (PEDOT:PSS), polyaniline (PANI), polypyrrole (PPy)). One or more of the composite materials described herein can be used in a variety of organic electronic, optical, and optoelectronic components (eg, organic thin film transistors (OTFTs), specifically organic field effect transistors (OFETs), as well as perceptrons, capacitors, unipolar circuits A specific circuit such as a complementary circuit (for example, an inverter circuit).

Other articles useful in the compounds of the invention are photovoltaic elements or solar cells. In particular, the polymers of the invention may exhibit broad optical absorption and/or regulated redox properties And ontobody carrier mobility, making it meet the expectations of such applications. For example, the polymers described herein can be used as a donor (p-type) semiconductor in the design of photovoltaic elements, including adjacent n-type semiconductor materials that form p-n junctions. The polymer can be in the form of a thin film semiconductor that can be deposited on a substrate to form a composite. The development of the polymers of the present invention in such elements is within the knowledge of those skilled in the art.

Accordingly, other aspects of the present invention are directed to a method of fabricating an organic field effect transistor incorporating a semiconductor material of the present invention. The semiconductor material of the present invention can be used to fabricate various types of organic field effect transistors, including top gate-top contact capacitor structures, top gate-bottom contact capacitor structures, bottom gate-top contact capacitor structures, and bottom gates. - Bottom contact capacitor structure. Figures 1a, 1b, 1c, and 1d show four common types of OFET structures: Figure 1a shows a bottom gate-top contact structure, Figure 1b shows a bottom gate-bottom contact structure, and Figure 1c shows a top gate-bottom contact structure. And Figure 11 shows the top gate-top contact structure. As shown in Figures 1a, 1b, 1c and 1d, the OFET can comprise a dielectric layer (e.g., 8, 8', 8" and 8" in Figures 1a, 1b, 1c and 1d, respectively), semiconductor/ Channel layers (eg, 6, 6', 6", and 6"' in Figures 1a, 1b, 1c, and 1d, respectively), gate contacts (eg, 10 in Figures 1a, 1b, 1c, and 1d, respectively) , 10', 10" and 10"'), the substrate (for example, 12, 12', 12" and 12"' in Figures 1a, 1b, 1c and 1d), source and gate contacts ( For example, they are represented by Figures 2a, 1b, 1c, and 1d as 2, 2', 2", 2"', 4, 4', 4", and 4"'), respectively.

In certain embodiments, an OTFT element can be fabricated on a doped germanium substrate using the semiconductor compound of the present invention, and SiO ₂ can be used as a dielectric in the top contact geometry. In a specific embodiment, in combination with the active semiconductor layer of at least one semiconductor compound of the present invention, deposition can be carried out at room temperature or elevated temperature. In other embodiments, the spin coating or printing described herein can be applied in conjunction with the active semiconductor layer of at least one semiconductor compound of the present invention. For top contact elements, a shadow mask can be used to pattern the metal contacts on top of the film.

In certain embodiments, an OTFT element can be fabricated on a plastic foil using the compound of the present invention, using a polymer as the dielectric in the top gate-bottom contact geometry. In a specific embodiment, the active semiconductor layer incorporating the at least one semiconductor compound of the present invention may be deposited at room temperature or elevated temperature. In other embodiments, the spin coating or printing described herein can be applied in conjunction with the active semiconductor layer of at least one semiconductor compound of the present invention. Gate and source/drain The touch can be made of Au, other metals or conductive polymers, deposited by vapor deposition and/or printing.

Similarly, other aspects of the invention relate to methods of fabricating an organic light-emitting transistor, an organic light-emitting diode (OLED) or an organic photovoltaic element in conjunction with one or more semiconductor materials of the present invention. 2 shows a representative structure of a bulk heterojunction organic photovoltaic element (also referred to as a solar cell) that can incorporate one or more semiconductor compounds of the present invention as a donor material. As shown, a representative solar cell typically includes a substrate 20 (eg, glass), an anode 22 (eg, ITO), a cathode 26 (eg, aluminum or calcium), and an active layer 24 between the anode and cathode, which may be combined with the present invention. One or more semiconductor compounds of the invention are used as electron donor (p-channel) materials. 3 shows a representative structure of an OLED that can be combined with one or more semiconductor compounds of the present invention as an electron transport and/or luminescent and/or hole transport material. As shown, the OLED typically includes a substrate 30 (not shown), a transparent anode 32 (eg, ITO), a cathode 40 (eg, a metal), and one or more organic layers that can incorporate one or more of the present invention. The semiconductor compound acts as a hole transport (n-channel) (layer 34 as shown) and/or luminescence (layer 36 as shown) and/or electron transport (p-channel) material (layer as shown) 38).

Molecular orbital (MO) calculations (B3LYP/6-31G*) (Spartan'08 Wavefunction, Inc., Irvine, CA) were performed to study the leading-edge molecular orbital energy and molecular orbitals of the dithiophene ethylenedithiazole units disclosed herein. Topology. The results are summarized in Table 1 below.

All publications cited in this specification, including but not limited to, patents and patent applications, are hereby incorporated by reference in their entirety as if individually individually individually individually individually individually individually

The invention includes other specific forms of embodiments that do not depart from the spirit or essential characteristics of the invention. The foregoing embodiments are therefore to be considered in all respects Therefore, the scope of the invention is intended to be embraced by the scope of the appended claims

Claims (23)

A semiconductor compound comprising one or more of the following formula (I): a group; wherein W is selected from the group consisting of S, Se, and Te; and each R ^{1 is} independently selected from the group consisting of H, halogen, -CN, NO ₂ , R ² , -LR ³ , OH, OR ² , OR ³ , NH ₂ , NHR ² , N(R ² ) ₂ , NR ² R ³ , N(R ³ ) ₂ , SH, SR ² , SR ³ , S(O) ₂ OH, -S(O) ₂ OR ² , -S(O) ₂ OR ³ , C(O)H, C(O)R ² , C(O)R ³ , C(O)OH, C(O)OR ² , C(O)OR ³ , C(O)NH ₂ , C(O)NHR ² , C(O)N(R ² ) ₂ , C(O)NR ² R ³ , C(O)N(R ³ ) ₂ , SiH ₃ , SiH a group of (R ² ) ₂ , SiH ₂ (R ² ) and Si(R ² ) ₃ , wherein L is selected from the group consisting of divalent C _1-40 alkyl, divalent C _2-40 alkenyl, divalent C _{1- a} group of ₄₀ haloalkyl groups and covalent bonds; each R ^{2 is} independently selected from the group consisting of C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl, and C _1-40 haloalkyl; Each R ^{3 is} independently selected from the group consisting of C _3-10 cycloalkyl, C _6-14 aryl, C _{6-14 haloaryl} , 3-12 membered heterocycloalkyl, and 5-14 membered heteroaryl groups. The groups may be optionally substituted with from 1 to 5 substituents selected from the group consisting of halogen, -CN, NO ₂ , R ² , OR ² and SR ² . The compound of claim 1, wherein one or more of the groups represented by the formula (I) is a dithiophene [1, 2, 3] represented by the formula (II) which is optionally substituted. Thiadiazole groups: The compound of claim 2, wherein R ¹ is selected from the group consisting of F, Cl, -CN, NO ₂ , R ² , OR ² and SR ² , and R ² is selected from a linear or branched chain. a C _1-40 alkyl, straight or branched C _2-40 alkenyl group and a linear or branched C _1-40 haloalkyl group. The compound according to claim 2, wherein R ¹ is H and the one or more groups represented by the formula (I) are unsubstituted dithieno[1, represented by the formula (III). 2,3]thiadiazole groups: The compound of claim 1, wherein the compound is a polymer having one or more first repeating units M ₁ , wherein the first constituent unit M ₁ has one or more formula (I) In the divalent unit shown, the polymer has a degree of polymerization (n) in the range of from 3 to 1,000. The compound of claim 5, wherein M ₁ is selected from the group consisting of: Wherein pi-2 is a conjugated polycyclic group which is optionally substituted; each occurrence of Ar is independently a 5- or 6-membered aryl or heteroaryl group which is optionally substituted; Z is a conjugated acyclic group a linker; m and m' are independently 0, 1, 2, 3, 4, 5 or 6, but at least one of m and m' is not 0; p and p' are independently 0 or 1, but p and p At least one of ' is 1. The compound of claim 6, wherein W is S. The compound of claim 6 or 7, wherein pi-2 is a selectively substituted C _8-26 aryl group or an 8-26 membered heteroaryl group. The compound of claim 8, wherein pi-2 is selected from the group consisting of: Wherein R ^a is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C(O)R, -OC(O)R, and -C(O)OR; R ^b Is selected from the group consisting of H, R and -LR ^f ; R ^c is H or R; R ^d is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C (O) R, -OC(O)R, -C(O)OR, and -LR ^f ; R ^e is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, - C(O)R, -OC(O)R, -C(O)OR and ^Rf ; ^Rf is a _C6-20 aryl group or a 5-20-membered aryl group, each of which may be optionally selected 1-8 base substitutions from the F, Cl, -CN, R, -OR, and -SR groups; L is selected from the group consisting of -O-, -S-, -C(O)-, -OC (O)-, -C(O)O- and a covalent bond; and R is selected from the group consisting of C _1-40 alkyl, C _1-40 haloalkyl, C _2-40 alkenyl, and C _{2 -40} alkynyl. A compound according to claim 6 or 7, wherein Ar in (Ar) _m and (Ar) _m' Wherein each X is independently selected from the group consisting of N, CH and CR ⁴ , wherein R ⁴ is selected from the group consisting of F, Cl, -CN, R ² , OR ² , SR ² , C(O)R ² , OC(O)R ² and C(O)OR ² , wherein R ² is selected from the group consisting of C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkynyl and C _1-40 haloalkyl Group. The compound of claim 10, wherein (Ar) _m and (Ar) _{m' are} independently selected from the group consisting of: Wherein each occurrence of R ⁴ is independently selected from the group consisting of F, Cl, CN, R ² , OR ² and SR ² , wherein R ² is a linear or branched C _1-40 alkyl or haloalkyl group. . The compound of claim 6 or 7, wherein Z is selected from the group consisting of: Wherein R ^{4 is} independently selected from the group consisting of F, Cl, CN, R ² , OR ² and SR ² , and R ² is selected from the group consisting of C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkyne And a C _1-40 haloalkyl group. The application of a compound according to any one of item 6 to item 12 patentable scope, further comprising one or more repeating units other than the M ₁ M _2, wherein the one or more repeating units selected from M ₂ The following groups: Wherein pi-2 is a selectively substituted conjugated polycyclic group; each occurrence of Ar is independently a selectively substituted 5- or 6-membered aryl or heteroaryl; Z is a conjugated acyclic linkage m; m and m' are independently 0, 1, 2, 3, 4, 5 or 6, but at least one of m and m' is not 0; m" is 0, 1, 2, 3, 4, 5 or 6; and p and p' are independently 0 or 1, but at least one of p and p' is 1. The compound of claim 13, wherein the one or more repeating units M ₂ , Z are selected from the group consisting of: (Ar) _m , (Ar) _{m '} and (Ar) _{m" are} independently selected from the following groups: Wherein R ^{4 is} independently selected from the group consisting of F, Cl, CN, R ² , OR ² and SR ² , and R ² is selected from the group consisting of C _1-40 alkyl, C _2-40 alkenyl, C _2-40 alkyne a group of C _1-40 haloalkyl groups; and pi-2 is selected from the group consisting of: Wherein R ^a is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C(O)R, -OC(O)R, and -C(O)OR; R ^b Is selected from the group consisting of H, R and -LR ^f ; R ^c is H or R; R ^d is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, -C (O) R, -OC(O)R, -C(O)OR, and -LR ^f ; R ^e is selected from the group consisting of H, F, Cl, -CN, R, -OR, -SR, - C(O)R, -OC(O)R, -C(O)OR and ^Rf ; ^Rf is a _C6-20 aryl group or a 5-20 membered heteroaryl group, each selected from the group consisting of F 1-8 base substitutions of the Cl, -C, -CN, R, -OR, and -SR groups; L is selected from the group consisting of -O-, -S-, -C(O)-, -OC(O -, -C(O)O- and a covalent bond; and R is selected from the group consisting of C _1-40 alkyl, C _1-40 haloalkyl, C _2-40 alkenyl, and C _2-40 Alkynyl. The compound of claim 14, wherein M ₁ is selected from the group consisting of: Wherein R ⁴ is selected from the group consisting of R ² , OR ² and SR ² , R ² is a linear or branched C _1-40 alkyl or haloalkyl group; and M ₂ is selected from the group consisting of Wherein (Ar) _m , (Ar) _{m '} and (Ar) _{m" are} independently selected from the group consisting of: The compound of claim 13, wherein the compound is a copolymer having a chemical formula selected from the group consisting of: Wherein M _1A and M _1B represent different repeating units M ₁ ; M _2A and M _2B represent different repeating units M ₂ ; x and y are real numbers representing the molar ratio; n is the degree of polymerization. The compound of claim 16, wherein the compound is a random copolymer. The compound of any one of claims 1 to 3, wherein the compound is a small molecule having a chemical formula selected from the group consisting of: Wherein Q ¹ and Q ^{2 are} independently selected from the group consisting of H, R ² and C(O)R ² , R ² is C _1-40 alkyl or haloalkyl; pi-2 is optionally substituted a conjugated polycyclic group; each occurrence of Ar is independently a 5- or 6-membered aryl or heteroaryl group which is optionally substituted; Z is a conjugated acyclic linker; m and m' are independently 0, 1, 2, 3, 4, 5 or 6, but at least one of m and m' is not 0; m" is 0, 1, 2, 3, 4, 5 or 6; p and p' are independently 0 or 1, but at least one of p and p' is 1. An electronic, optical or optoelectronic component comprising a semiconductor component, wherein the semiconductor component comprises a compound according to any one of claims 1 to 18. An organic photovoltaic element comprising: an anode, a cathode, optionally one or more anode intermediate layers, optionally one or more cathode intermediate layers, and a semiconductor member interposed between the anode and the cathode, wherein the semiconductor The member includes a mixed material including a compound that receives electrons and a compound that supplies electrons, and the compound that supplies electrons is The compound of any one of items 1 to 18. The element of claim 20, wherein the electron accepting compound is a fullerene compound. The element of claim 20, wherein the electron-donating compound is an electron transporting polymer. An organic thin film transistor comprising a substrate, a thin film semiconductor, a dielectric layer, a gate electrode, and source and drain electrodes, wherein the thin film semiconductor includes any one of items 1 to 18 of the patent application scope The compound described in the item.